CN109589882B - Amphiphilic silica aerogel composite material for wastewater treatment - Google Patents
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Abstract
The invention discloses an amphiphilic silica aerogel composite material for wastewater treatment, which is obtained by compounding citric acid grafted chitosan and silicic acid solution under the catalysis of a silane coupling agent, wherein the tap density of the amphiphilic silica aerogel composite material is 0.15-0.30g/cm3Specific surface area:>600 m2(iv)/g, toluene oil absorption:>3 g/g; the composite material belongs to a high-end silicon-based nano porous material, citric acid grafted chitosan with hydrophilic groups is compounded with silica aerogel to prepare the composite aerogel with both hydrophilic and oleophilic characteristics, the adsorption rates of the composite aerogel on water and oily material toluene are respectively up to 520% and 485%, and the composite aerogel also has the characteristics of large specific surface area, high porosity, good pore diameter connectivity and the like, and is very suitable for adsorption and deep treatment of oily substances in water, especially emulsified oil pollutants.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to an amphiphilic silica aerogel composite material for wastewater treatment.
Background
The aerogel is obtained by a sol-gel process, has a three-dimensional network structure, has a nanometer-level skeleton and nanometer-level holes, and is filled with gasLightweight nanoporous materials, typically represented by silica aerogels, have low density (0.00016-0.3 g/cm)3) Large specific surface area (200- & lt2000 & gt m- & lt2The material has the characteristics of low thermal conductivity (the room temperature thermal conductivity is 0.013W/m.K) and the like, and has wide application prospects in various fields such as heat insulation, adsorption, medicine carrying, catalysis, solar cells and the like. Particularly, the aerogel material has much higher performance than the traditional nano powder material (such as Degussa P25 type TiO)2Nano powder: BET-55m2The specific surface area of the porous material/g) and the microstructure characteristics of high pore volume and open pores are very suitable for adsorbing various toxic and harmful organic matters or heavy metal ions which pollute the environment and harm the health of human bodies, and the porous material has the advantages of large adsorption capacity, high adsorption speed and easy recovery and treatment, thereby showing important application potential and huge market space.
The aerogel can be made of various materials, such as silicon oxide, titanium oxide, carbon, graphene, cellulose and the like, wherein the silicon oxide aerogel is the aerogel class which is the earliest research (1930), the most mature in the current process and the most promising in application prospect, has the advantages of good high temperature resistance, low thermal conductivity, wide raw material sources, relatively simple preparation process and the like, and is always a focus of academic, industrial and investment circles. The main problems encountered in the application and popularization of the current aerogel materials in the market are: (1) the price is high, and the price of partial powder products is up to 300 ten thousand yuan per ton; (2) the product form is single, the product is a super-hydrophobic powder and a glass fiber composite felt/board, and the product homogeneity of different enterprises is serious; (3) the application technology is lacked, and due to the specific super-hydrophobic property of the aerogel, the product is difficult to be matched with other materials, components or use environments, or the problems of dust pollution, complex construction, poor durability and the like are caused, so that a great number of potential customers can only expect the 'glue' exclamation. Taking wastewater treatment as an example: the aerogel has much higher specific surface area and higher pore volume than the traditional silicon-based materials (such as silicon oxide nano powder), is very suitable to be used as a wastewater treatment material, adsorbs oily pollutants (such as benzene, toluene and phenol) in wastewater and adsorbs heavy metal ions (such as Pb) which cause great harm to the ecological environment2+、Cd2+、Hg2+). However, the present oxygenThe silica aerogel products are in a super-hydrophobic state and are difficult to be compatible with a water-based system; and pollutants such as emulsified oil, heavy metal ions and the like in the wastewater are all in a water-soluble state, and the hydrophobic aerogel cannot be used. Therefore, a novel aerogel surface modification technology is developed, so that the aerogel surface modification technology can have hydrophilic characteristics on the basis of keeping hydrophobicity, high pore volume and high specific surface area, is compatible with an aqueous service environment, and has important research and practical values.
In the field of wastewater treatment, enterprises have a very urgent need for new materials, especially physical adsorption materials capable of deeply treating emulsified oil. The oily wastewater mainly comes from industrial departments of petroleum, petrochemical industry, steel, coking, gas generation stations, machining and the like, and has wide sources and complex components. If the waste oil is not recycled, not only is the resource wasted, but also serious harm is caused to water bodies, aquatic organisms, soil, crops, livestock and the like, and even carcinogenic hydrocarbon contained in the waste oil can be enriched by fish and shellfish and harm human health through a food chain. The oil species in wastewater are generally present in three states: floating oils, dispersed oils, and emulsified oils, which are the most difficult of the three. Unlike the first two types of oil, the emulsified oily sewage contains a surfactant, so that the oil becomes an emulsion, the oil drop has extremely small particle size (generally less than 10 μm, and most of the oil drop is 0.1-2 μm), and the emulsified oily sewage has strong stability in dynamics and is generally difficult to treat. The emulsion has high organic content, CODCr is usually tens of thousands mg/L, and the components of the emulsion are not only emulsified oil, but also contain a large amount of surfactant and other additives. Although the conventional oil removal method (such as salting-out-air flotation-adsorption, demulsification-coagulation-air flotation, oil separation-micro flocculation and the like) can remove floating oil and dispersed oil with larger particle sizes, the obtained effluent oil content is only dozens of mg/L, but the effect on emulsified oil is poor, the CODCr value of the effluent is still as high as hundreds to thousands of mg/L, the discharge requirement cannot be met, and the subsequent treatment is required. Among several post-treatment methods such as adsorption, membrane separation, nanofiltration and the like, the physical adsorption method is an advanced treatment method with higher cost performance. However, the existing common adsorption materials such as activated carbon, high oil absorption resin, fly ash, bentonite and the like have the problems of high price, low oil absorption speed, difficult regeneration, secondary pollution of adsorption oil and the like, the treatment efficiency is low, the cost performance is poor, and the development of a novel efficient adsorption material is urgently needed.
Disclosure of Invention
The invention aims to provide an amphiphilic silica aerogel composite material for wastewater treatment, which has unique hydrophilic and oleophilic characteristics, has good compatibility with a water system using environment, has the characteristics of large specific surface area, high porosity, good pore diameter connectivity and the like, and is very suitable for adsorption and advanced treatment of oily substances in water, particularly emulsified oil pollutants in wastewater.
The purpose of the invention can be realized by the following technical scheme:
an amphiphilic silica aerogel composite material for wastewater treatment is prepared by compounding citric acid grafted chitosan and silicic acid solution under the catalysis of a silane coupling agent, and the tap density of the amphiphilic silica aerogel composite material is 0.15-0.30g/cm3Specific surface area:>600 m2(iv)/g, toluene oil absorption:>3g/g。
further, the preparation method of the amphiphilic silica aerogel composite material comprises the following steps:
first step, grafting chitosan with citric acid
Dissolving 1g of chitosan in 100ml of 2% formic acid solution to prepare chitosan solution; dissolving citric acid in a DMF solution to prepare a 20-35% citric acid solution, mixing the citric acid solution with a chitosan solution, adding HOBT/EDCI and triethylamine, stirring for 2 hours at 35-40 ℃, adjusting the pH of the solution to 7.5-8.0, separating out a precipitate, filtering, washing with purified water to obtain citric acid grafted chitosan, dissolving the washed citric acid grafted chitosan in 100ml of a 2% formic acid solution, and preparing a chitosan solution for later use;
second step preparation of silicic acid solution
Selecting 20 ml of industrial water glass with the modulus of 3.0, adding the industrial water glass into 100ml of purified water, mixing and stirring for 20-30min, then adding 100g of strong-acid ion exchange resin, stirring for 5min, and filtering to remove filter residues to obtain a silicic acid solution;
the third step: preparation of amphiphilic silica aerogel composite
And mixing and coupling the chitosan solution prepared in the first step and the silicic acid solution prepared in the second step, and dehydrating and drying to obtain the amphiphilic silicon dioxide aerogel composite material.
Further, the amount of HOBT/EDCI added was 0.3 times the molar amount of citric acid, and the amount of triethylamine added was 0.5 times the molar amount of citric acid.
Further, the structural formula of the citric acid grafted chitosan is shown as a formula:
wherein the deacetylation degree of the chitosan powder is 80-98%.
Further, the third step of preparing the amphiphilic silica aerogel composite material comprises the following specific steps:
s1, mixing the chitosan solution with the silicic acid solution, and stirring for 15-20min to obtain a silicic acid-chitosan mixed solution;
s2, adding an isobutyl triethoxy silane coupling agent into the silicic acid-chitosan mixed solution, uniformly stirring, and reacting at 70-75 ℃ for 7-10h to obtain silicon oxide-chitosan composite gel;
s3, drying the silica-chitosan composite gel prepared in the step S2 at 45 ℃ for 10-15 hours, cooling to room temperature, mashing to a particle size smaller than 0.8cm, immersing the mashed silica-chitosan composite gel into dioxane, and stirring to enable the dioxane to replace water in the silica-chitosan composite gel;
s4, immersing the silicon oxide-chitosan composite gel replaced in the step S3 into petroleum ether, and stirring to enable the petroleum ether to replace dioxane in the silicon oxide-chitosan composite gel;
s5, placing the silicon oxide-chitosan composite gel which is replaced in the step S4 into a drying box, and drying for 10-12h at the temperature of 105-110 ℃ under normal pressure to obtain the amphiphilic silicon dioxide aerogel composite material.
The invention has the beneficial effects that:
(1) the invention provides an amphiphilic silica aerogel composite material for wastewater treatment, which belongs to a high-end silicon-based nano porous material, citric acid grafted chitosan with hydrophilic groups is compounded with silica aerogel to prepare composite aerogel with both hydrophilic and oleophilic characteristics, the adsorption rates of the composite aerogel on water and oily material methylbenzene are respectively as high as 520% and 485%, compared with the traditional silica aerogel product only with hydrophobic characteristics in the current market, the product has unique hydrophilic and oleophilic characteristics, is good in compatibility with a water system using environment, has the characteristics of large specific surface area, high porosity, good pore diameter connectivity and the like, and is very suitable for adsorption and deep treatment of oily substances in water, particularly emulsified pollutants. In addition, the prepared amphiphilic silica aerogel composite material also has strong heavy metal ions (Pb)2+、Cu2+) The removal capacity can be used for deep purification of chemical wastewater and adsorption of lead ions in the wastewater, the limit adsorption amount is up to 407mg/g, the lead ions are positioned at the top level in a plurality of lead ion adsorption materials, and the lead ions have great application potential in the aspect of heavy metal ion adsorption due to the advantage of low cost;
in addition, the chitosan grafted by citric acid greatly increases the antibacterial performance of the chitosan, is beneficial to removing microorganisms in wastewater, and the introduced carboxyl can be connected with a silicon-oxygen bond under the action of a silane coupling agent to increase coordination sites, so that the coordination capacity with heavy metal ions is enhanced, and the removal of the heavy metal ions is accelerated;
(2) the amphiphilic silica aerogel composite material is mixed with 50 percent acrylic emulsion or machining emulsified oil wastewater, and the mixture is stirred for 5 minutes to realize the mixing of oily materials, surfactants, organic additives and heavy metal ions (Pd) in water2+、Cu2+) The transmittance of the filtrate in a visible light region is basically consistent with that of pure water, and the infrared spectrum of the filtrate is consistent with that of water. COD test shows that the purification effect of the amphiphilic aerogel on high-concentration emulsified oil wastewater is more than 96 percent, which is 9 times that of the traditional activated carbon adsorption material.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
An amphiphilic silica aerogel composite material for wastewater treatment is obtained by compounding citric acid grafted chitosan and a silicic acid solution under the catalysis of a silane coupling agent, and the preparation method of the specific amphiphilic silica aerogel composite material comprises the following steps:
first step, grafting chitosan with citric acid
The reaction formula is as follows:
dissolving 1g of chitosan in 100ml of 2% formic acid solution to prepare chitosan solution; dissolving citric acid in a DMF solution to prepare a 20% citric acid solution, mixing the citric acid solution with a chitosan solution, and adding HOBT/EDCI and triethylamine, wherein the addition amount of the HOBT/EDCI is 0.3 times of the molar amount of the citric acid, and the addition amount of the triethylamine is 0.5 times of the molar amount of the citric acid; stirring for 2h at 35 ℃, adjusting the pH of the solution to 7.50, separating out a precipitate, filtering, washing with purified water to obtain citric acid grafted chitosan with a structure shown in formula a, and dissolving the washed precipitate in 100ml of 2% formic acid solution to prepare a chitosan solution;
infrared characterization of citric acid grafted chitosan a: IR (KBr):
=3510（-OH）,3475（-COOH）,3273（-CONH-）,2928（-CH2-）,1736,1708(-COO-)。
second step preparation of silicic acid solution
Selecting 20 ml of industrial water glass with the modulus of 3.0, adding the industrial water glass into 100ml of purified water, mixing and stirring for 20min, adding strong-acid ion exchange resin, stirring for 5min, and filtering to remove filter residues to obtain a silicic acid solution;
the third step: preparation of amphiphilic silica aerogel composite
S1, mixing the chitosan solution with the silicic acid solution, and stirring for 20min to obtain a silicic acid-chitosan mixed solution;
s2, adding an isobutyl triethoxy silane coupling agent into the silicic acid-chitosan mixed solution, uniformly stirring, and reacting at 70 ℃ for 7 hours to obtain silicon oxide-chitosan composite gel;
s3, drying the silica-chitosan composite gel prepared in the step S2 at 45 ℃ for 10 hours, cooling to room temperature, mashing to a particle size smaller than 0.8cm, immersing the mashed silica-chitosan composite gel into dioxane, and stirring to enable the dioxane to replace water in the silica-chitosan composite gel;
s4, immersing the silicon oxide-chitosan composite gel replaced in the step S3 into petroleum ether, and stirring to enable the petroleum ether to replace dioxane in the silicon oxide-chitosan composite gel;
and S5, putting the silicon oxide-chitosan composite gel replaced in the step 4 into a drying oven, and drying at 105 ℃ for 12 hours under normal pressure to obtain the amphiphilic silicon dioxide aerogel composite material. The tap density is 0.25 g/cm through a BET isothermal adsorption test3Specific surface area: 933.2 m2(iv)/g, toluene oil absorption: 4.8 g/g.
Example 2
An amphiphilic silica aerogel composite material for wastewater treatment is obtained by compounding citric acid grafted chitosan and a silicic acid solution under the catalysis of a silane coupling agent, and the preparation method of the specific amphiphilic silica aerogel composite material comprises the following steps:
first step, grafting chitosan with citric acid
Dissolving 1g of chitosan in 100ml of 2% formic acid solution to prepare chitosan solution; dissolving citric acid in a DMF solution to prepare a 35% citric acid solution, mixing the citric acid solution with a chitosan solution, and adding HOBT/EDCI and triethylamine, wherein the addition amount of the HOBT/EDCI is 0.3 times of the molar amount of the citric acid, and the addition amount of the triethylamine is 0.5 times of the molar amount of the citric acid; stirring for 2h at 40 ℃, adjusting the pH of the solution to 8.0, separating out a precipitate, filtering, and washing with purified water to obtain the citric acid grafted chitosan with the structure of the formula a, wherein the reaction formula is as follows:
dissolving the washed precipitate in 100ml of 2% formic acid solution to prepare chitosan solution;
second step preparation of silicic acid solution
Selecting 20 ml of industrial water glass with the modulus of 3.0, adding the industrial water glass into 100ml of purified water, mixing and stirring for 20min, adding strong-acid ion exchange resin, stirring for 5min, and filtering to remove filter residues to obtain a silicic acid solution;
the third step: preparation of amphiphilic silica aerogel composite
S1, mixing the chitosan solution with the silicic acid solution, and stirring for 15min to obtain a silicic acid-chitosan mixed solution;
s2, adding an isobutyl triethoxy silane coupling agent into the silicic acid-chitosan mixed solution, uniformly stirring, and reacting at 75 ℃ for 10 hours to obtain silicon oxide-chitosan composite gel;
s3, drying the silica-chitosan composite gel prepared in the step S2 at 45 ℃ for 10 hours, cooling to room temperature, mashing to a particle size smaller than 0.8cm, immersing the mashed silica-chitosan composite gel into dioxane, and stirring to enable the dioxane to replace water in the silica-chitosan composite gel;
s4, immersing the silicon oxide-chitosan composite gel replaced in the step S3 into petroleum ether, and stirring to enable the petroleum ether to replace dioxane in the silicon oxide-chitosan composite gel;
s5, putting the silicon oxide-chitosan composite gel replaced in the step 4 into a drying boxAnd drying at the normal pressure and the temperature of 110 ℃ for 10 hours to obtain the amphiphilic silica aerogel composite material. The tap density is 0.18 g/cm through a BET isothermal adsorption test3Specific surface area: 896.2 m2(iv)/g, toluene oil absorption: 3.5 g/g.
Example 3
An amphiphilic silica aerogel composite material for wastewater treatment is obtained by compounding citric acid grafted chitosan and a silicic acid solution under the catalysis of a silane coupling agent, and the preparation method of the specific amphiphilic silica aerogel composite material comprises the following steps:
first step, grafting chitosan with citric acid
The reaction formula is as follows:
dissolving 1g of chitosan in 100ml of 2% formic acid solution to prepare chitosan solution; dissolving citric acid in a DMF solution to prepare a 30% citric acid solution, mixing the citric acid solution with a chitosan solution, and adding HOBT/EDCI and triethylamine, wherein the addition amount of the HOBT/EDCI is 0.3 times of the molar amount of the citric acid, and the addition amount of the triethylamine is 0.5 times of the molar amount of the citric acid; stirring for 2h at 38 ℃, adjusting the pH of the solution to 7.6, separating out a precipitate, filtering, washing with purified water to obtain citric acid grafted chitosan with a structure shown in formula a, and dissolving the washed precipitate in 100ml of 2% formic acid solution to prepare a chitosan solution;
second step preparation of silicic acid solution
Selecting 20 ml of industrial water glass with the modulus of 3.0, adding the industrial water glass into 100ml of purified water, mixing and stirring for 25min, adding strong-acid ion exchange resin, stirring for 5min, and filtering to remove filter residues to obtain a silicic acid solution;
the third step: preparation of amphiphilic silica aerogel composite
S1, mixing the chitosan solution with the silicic acid solution, and stirring for 19min to obtain a silicic acid-chitosan mixed solution;
s2, adding an isobutyl triethoxy silane coupling agent into the silicic acid-chitosan mixed solution, uniformly stirring, and reacting at 73 ℃ for 9 hours to obtain silicon oxide-chitosan composite gel;
s3, drying the silica-chitosan composite gel prepared in the step S2 at 45 ℃ for 11 hours, cooling to room temperature, mashing to a particle size smaller than 0.8cm, immersing the mashed silica-chitosan composite gel into dioxane, and stirring to enable the dioxane to replace water in the silica-chitosan composite gel;
s4, immersing the silicon oxide-chitosan composite gel replaced in the step S3 into petroleum ether, and stirring to enable the petroleum ether to replace dioxane in the silicon oxide-chitosan composite gel;
and S5, putting the silicon oxide-chitosan composite gel replaced in the step 4 into a drying oven, and drying for 11 hours at 106 ℃ under normal pressure to obtain the amphiphilic silicon dioxide aerogel composite material. The tap density is 0.28 g/cm through a BET isothermal adsorption test3Specific surface area: 908.6m2(iv)/g, toluene oil absorption: 4.1 g/g.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (3)
1. The amphiphilic silica aerogel composite material for wastewater treatment is characterized in that: the material is obtained by compounding citric acid grafted chitosan and silicic acid solution under the catalysis of a silane coupling agent, and the tap density of the amphiphilic silicon dioxide aerogel composite material is 0.15-0.30g/cm3Specific surface area:>600m2(iv)/g, toluene oil absorption:>3g/g；
the preparation method of the amphiphilic silica aerogel composite material comprises the following steps:
first step, grafting chitosan with citric acid
Dissolving 1g of chitosan in 100ml of 2% formic acid solution to prepare chitosan solution; dissolving citric acid in a DMF solution to prepare a 20-35% citric acid solution, mixing the citric acid solution with a chitosan solution, adding HOBT/EDCI and triethylamine, stirring for 2 hours at 35-40 ℃, adjusting the pH of the solution to 7.5-8.0, separating out a precipitate, filtering, washing with purified water to obtain citric acid grafted chitosan, dissolving the washed citric acid grafted chitosan in 100ml of a 2% formic acid solution, and preparing a chitosan solution for later use;
the structural formula of the citric acid grafted chitosan is shown as a formula:
wherein the deacetylation degree of the chitosan powder is 80-98%;
second step preparation of silicic acid solution
Selecting 20 ml of industrial water glass with the modulus of 3.0, adding the industrial water glass into 100ml of purified water, mixing and stirring for 20-30min, then adding 100g of strong-acid ion exchange resin, stirring for 5min, and filtering to remove filter residues to obtain a silicic acid solution;
the third step: preparation of amphiphilic silica aerogel composite
And mixing and coupling the chitosan solution prepared in the first step and the silicic acid solution prepared in the second step, and dehydrating and drying to obtain the amphiphilic silicon dioxide aerogel composite material.
2. An amphiphilic silica aerogel composite for wastewater treatment according to claim 1, characterized in that: the amount of HOBT/EDCI added was 0.3 times the molar amount of citric acid, and the amount of triethylamine added was 0.5 times the molar amount of citric acid.
3. An amphiphilic silica aerogel composite for wastewater treatment according to claim 1, characterized in that: the third step is to prepare the amphiphilic silica aerogel composite material by the following specific steps:
s1, mixing the chitosan solution with the silicic acid solution, and stirring for 15-20min to obtain a silicic acid-chitosan mixed solution;
s2, adding an isobutyl triethoxy silane coupling agent into the silicic acid-chitosan mixed solution, uniformly stirring, and reacting at 70-75 ℃ for 7-10h to obtain silicon oxide-chitosan composite gel;
s3, drying the silica-chitosan composite gel prepared in the step S2 at 45 ℃ for 10-15 hours, cooling to room temperature, mashing to a particle size smaller than 0.8cm, immersing the mashed silica-chitosan composite gel into dioxane, and stirring to enable the dioxane to replace water in the silica-chitosan composite gel;
s4, immersing the silicon oxide-chitosan composite gel replaced in the step S3 into petroleum ether, and stirring to enable the petroleum ether to replace dioxane in the silicon oxide-chitosan composite gel;
s5, placing the silicon oxide-chitosan composite gel which is replaced in the step S4 into a drying box, and drying for 10-12h at the temperature of 105-110 ℃ under normal pressure to obtain the amphiphilic silicon dioxide aerogel composite material.
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| CN107583620A (en) * | 2017-10-23 | 2018-01-16 | 黄淮学院 | A kind of chitosan-based metal ion adsorbent and preparation method thereof |
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